Sulfonate mixtures based on derivatives of olefins of the vinyl,vinylidene and internal types having from 12 to 16 carbon atoms per molecule

ABSTRACT

IT IS DISCLOSED THAT OLEFIN SULFONATES OBTAINED BY SAPONIFYING THE REACTION PRODUCT OF SO3 AND OLEFINS HAVING FROM ABOUT 12 TO ABOUT 16 CARBON ATOMS PER MOLECULE PROVIDE EXCELLENT HARD WATER DETERGENT MATERIALS WHEN THE OLEFINS ARE PREDOMINANTLY UNBRANCHED ACYCLIC TERMINAL MONOOLEFINS IN ADMIXTURE WITH FROM ABOUT 3 TO ABOUT 30 MOL PERCENT OF BETA-BRANCHED TERMINAL OLEFINS AND FROM ABOUT 3 TO ABOUT 12 MOL PERCENT OF INTERNAL OLEFINS. PREFERRED OLEFIN SULFONATES ARE THE SODIUM AND POTASSIUM SLATS OF ALKENE SULFONIC ACIDS AND OF HYDROXY ALKANE SULFONIC ACIDS. THE MIXTURES OF THE PRESENT INVENTION INVOLVE SULFONATES WITH FROM ABOUT 64 TO ABOUT 97 PERCENT C16, FROM ZERO TO ABOUT 15 PERCENT C14 AND FROM ABOUT 3 TO ABOUT 33 PERCENT C12 CARBON ATOMS PER MOLECULE, IN PERCENT BY WEIGHT.

Dec. 25, 1973 M TUVELL ETAL. 3,781,339

SULFONATE MIXTURES BASED ON DERIVATIVES OF OLEFINS OF THE VINYL,VINYLIDENE AND INTERNAL TYPES HAVING FROM 12 TO 16 CARBON ATOMS PERMOLECULE Filed Nov. 2, 1970 United States Patent O 260513 R 7 Claims 10Us. Cl.

ABSTRACT on THE DISCLOSURE It is disclosed that olefin sulfonatesobtained by saponifying the reaction product of S0 and olefins havingfrom about 12 to about 16 carbon atoms per molecule provide excellenthard water detergent materials when the olefins are predominantlyunbranched acyclic terminal morro olefins in admixture with from about 3to about 30 mol percent of beta-branched terminal olefins and from about20 3 to about 12 mol percent of internal olefins. Preferred olefinsulfonates are the sodium and potassium salts of alkene sulfonic acidsand of hydroxy alkane sulfonic acids. The mixtures of the presentinvention involve sulfonates with from about 64 to about 97 percent Cfrom zero to about 15 percent C and from about 3 to about 33 percent Ccarbon atoms per molecule, in percent by 'weight.

BACKGROUND OF THE INVENTION Field of the invention Description of theprior art Alpha olefin sulfonates are will known in the prior art asbeing readily produced by the reaction of alpha olefins with S0 or withcompounds or complexes containing or yielding S0 Of particular interestis the reaction with uncomplexed S0 The reaction is followed bysaponification with a caustic or alkaline substance such as a hydroxide,oxide or carbonate of the alkali or alkaline earth metals, such as NaOHand KOH, to produce water solu- .-'ble metal salts. These products haveuseful properties for various washing purposes such as cleansingfabrics, skin and dishes. The carbon skeletal structures of thesulfonates are basically isomeric unsaturated and hydroxy saturatedisomers having carbon skeletons similar to the starting olefins.Typically, RCHgCH CH CH=CH reacte starting olefins. Typically, RCH CH CHCH=CH reacted with 80;, produces predominantly compounds of theformulas:

v j 'The prior art teaches generally that such sulfonates 70 ,canbeproduced on a basis of olefins of various carbon skeletalconfigurations having 10 to 24, more or less, carbon atoms per molecule.For the most part, the prior art preference is for the use of olefinshaving a single molecular structural configuration, particularlystraight chain olefins of the alpha type and for olefins that have 16 ormore, preferably 18 or more, carbon atoms per molecule. Thus in theprior art, R of the foregoing formulae is generally a straight chainsaturated alkyl group having 5 to 19', more or less, carbon atoms,particularly 11 or more, preferably 13. In some instances olefins havebeen used that were different .from such straight chain olefins. Theplurally branched propylene tetramer, for example, has been mentioned.Internal olefins and vinylidene olefins, individually, have beenmentioned in a general way but for the most part there is no teaching ofsynergism in sulfonate mixtures based on mixed olefins.

SUMMARY OF THE INVENTION The present invention provides synergisticcompositions of olefin sulfonates of certain mixed structures and of aspecific narrow range of molecular weights, expressed as a specific areaon the proportions plot of the figure which have excellent detergentproperties, particularly as regards solubility and cleaning ability evenin hard water. The materials are useful for washing porous materialssuch as fabrics; surfaces of living organisms, typically the skin andhair of human beings or lower animals; and for washing materials havinghard, comparatively impervious, surfaces such as sheet metal or plasticsin various forms including but not limited to dishes and silverware. Thematerials are useful at intermediate temperatures at low temperaturessuch as 2030 C., as well as at hot water temperatures, typically to 100C. or higher, and at atmospheric pressure or higher or lower pressures.Utility under such a wide variety of conditions permits a singlecomposition to be used for most if not all cleaning applications for anentire family or business establishment, for example.

DESCRIPTION OF THE DRAWING The single figure of the drawing is a ternarydiagram showing the properties of various olefin sulfonate compositions.Equal-effectiveness lines for various compositions are shown based oncomparison with a standard detergent system. The present inventionrelates to the compositions in the area A-B-C-DEF-GA of the figure.

DESCRIPTION OF THE PREFERRED EMBODIMENTS In accordance with the presentinvention, olefin sulfonates are provided which are based on thesaponified products of sulfonation of monoolefin mixtures having fromabout 12 to about 16 carbon atoms per molecule and averaging from about14.7 to about 15.9 carbon atoms per molecule. A narrower preferred rangeis based on the saponified product of the sulfonation of mixtures ofmonoolefins having mainly 12 and 16 carbon atoms per molecule containingfrom zero to about 15 wt. percent sulfonates having 14 carbon atoms permolecule. Preferred olefins range from about 60 to about 98 mol percentvinyl, from about 1 to about 30 mol percent vinylidene and from about 1to about 15 mol percent "internal olefins. Olefins sulfonated mayinclude C C C C C or mixtures provided that the mixtures meet theforegoing requirements. Of these, preferred olefins are those containingeven numbers of carbon atoms per molecule.

Such olefins are preferably produced by chain growth with ethylene ontriethyl aluminum.

In typical preferred olefin mixtures, the C olefins are from about toabout 98 mol percent vinyl and from about 1 to about 7 percent each ofvinylidene and internal olefins. The C olefins are from about 80 toabout 90 mol percent vinyl, from about 5 to about 12% each of vinylideneand internal olefins. The C olefins are from about 60 to about 70 molpercent vinyl, from about 20 to about 30% vinylidene and from about 5 toabout 15% internal olefins.

When such mixtures of olefins are reacted with S and saponified withNaOH, for example, the products are principally isomeric spectra ofalkene sulfonic acid sodium salts, hydroxy alkane sulfonic acid sodiumsalts, alkene disulfonic acid disodium salts and hydroxy alkanedisulfonic acid disodium salts. Similarly, Where the saponification iswtih caustic potash the products are potassium salts of these acids.These compounds are termed olefin sulfonates. They are exemplified (assodium salts) by the basic formulas:

where R, R and R" are H or alkyl (C H and wherein the total number ofcarbon atoms in R, R and R" is predominantly 7, 9 and 11.

Additional components which may be present in trace amounts includetrisulfonates and higher order sulfonates. The ratios of the varioussulfonates of these categories normally present on a weight basis in theproducts of this invention are from about 30 to about 70 percent ofalkene sulfonates, from about 20 to about 70 percent of hydroxy alkanesulfonates, from about 2 percent to about 15 percent of thedisulfonates, and about 1 percent or less of trisulfonates, etc., suchpolysulfonates containing approximately equal amounts of alkane andhydroxy alkane compounds.

The foregoing sulfona-te compounds are believed to be the result of theformation and cleavage of sultone intermediates. Such sultoneintermediates form preferentially as rings with a specific number ofatoms per ring, typically 5. Ratings of other numbers of atoms such as 4and 6 are formed generally in lesser proportions. On hydrolysis thesultones open to provide the alkene sulfonates and hydroxy alkanesulfonates where the location of the unsaturation and hydroxyl groupsdepend to a large extent upon the number of atoms in the rings of theintermediate sultones. Some further ramification of the distribution ofthe various forms arises through isomerization. Thus, it ischaracteristic of the alkane sulfonates that they have predominantly 2-3unsaturation (30-70 percent) with some 1-2 unsaturation (10-25 percent),some 3-4 unsaturation (-25 percent), some 4-5 unsaturation (5- percent)and so on. Similarly, it is characteristic of the hydroxy alkanesulfonates that they are predominantly 3-hydroxy compounds (about 50-70percent) with lesser amounts of 2-hydroxy, 4-hydroxy and S-hydroxycompounds. The disulfonates, trisulfonates may be regarded as the resultof the reaction of a second molecule of S0 with the double bond of analkene sulfonate precursor and hence involving further ramifications asseveral spectra based on the spectra of alkene sulfonates.

It is evident that the hydrocarbon structures of the various compoundsexemplified are principally constituted by a ramified substituentcontaining portion or radical having about 5 carbon atoms connnected toa long unsubstituted hydrocarbon radical. In general, the lengthvariation of the unsubstituted radical is small over the range of 12-16total carbon atoms per molecule, thus it is not essential that therelative proportions of vinyl, vinylidene and internal olefin structuresbe the same for all starting olefins or the resultant products. Althoughsuch similarity of distributions for the various molecular weights ispreferred in some instances, it is preferred in some instances thatthere be a higher percentage of non-vinyl molecular structures in the Cstarting olefins than in the C starting olefins thereby maintaining agreater degree of similarity in the number of carbon atoms in the longunsubstituted hydrocarbon radical. Y

Examples of typical compounds in the mixtures 'described herein includethe following.

tetradec-1,2-ene-1-sulfonic acid sodium salt hexadec-1,2-ene-l-sulfonicacid potassium salt dodec-1,2-ene-1-sulfonic acid sodium salttetradec-2,3-ene-l-sulfonic acid sodium salt hexadec-2,3-ene-l-sulfonicacid sodium salt tetradec-3,4-ene-1-sulfonic acid potassium salthexadec-3,4-ene-l-sulfonic acid sodium salt dodec-3,4-ene-1-sulfonicacid sodium salt tetradec-4,5-ene-l-sulfonic acid sodium salthexadec-4,5-ene-l-sulfonic acid sodium salt2-ethyl-dodec-1,2-ene-1-sulfonic acid sodium saltZ-butyl-decyl-1,2-ene-1-sulfonic acid sodium saltZ-hexyl-oct-l,2-ene-1-sulfonic acid potassium saltZ-ethyI-tetradec-1,2-ene-1-sulfonic acid sodium saltZ-butyl-dodec-1,2-ene-1-sulfonic acid sodium saltZ-hexyl-dec-l,2-ene-l-sulfonic acid sodium salttetradec-3,4-ene-3-sulfonic acid sodium salt hexadec-3,4-ene-3-sulfonicacid sodium salt tetradec-6,7-ene-6-sulfonic acid sodium salthexadec-6,7-ene-6-sulfonie acid potassium salt 4-ethyl-dodec-3,4-ene-3sulfonic acid sodium salt 4-ethyl-tetradec-3,4-ene-3-sulfonic acidsodium salt undec-7,8-ene-5-(1'-ethyl methylene sulfonic acid potassiumsalt) tridec-7,8-ene-5-(1-ethyl methylene sulfonic acid sodium salt)tetradec-3,4-ene-1,2-disulfonic acid-disodium salthexadec-3,4-ene-1,2-disulfonic acid-disodium salt undec-6,7-ene-5-sodiumsulfonate-S- l-ethyl-methylene potassium sulfonate)tridec-6,7-ene-5-sodium sulfonate-5-(1-ethyl-methylene sodium sulfonate)tetradec-4,5-ene-1,2-disulfonic acid-disodium salt Examples of othertypical compounds in the mixtures described herein include thefollowing.

tetradec-Z-ol-l-sulfonic acid sodium salt hexadec-Z-ol-l-sulfonic acidsodium salt tetradec-3-ol-1-sulfonic acid sodium salthexadec-S-ol-l-sulfonic acid sodium salt tetradec-4-ol-l-sulfonic acidpotassium salt hexadec-4-ol-1-sulfonic acid sodium salttetradec-S-ol-l-sulfonic acid sodium salt hexadec-S-ol-l-sulfonic acidsodium salt 2-ethyl-dodec-2-ol-l-sulfonic acid sodium salt2-butyl-decyl-3-ol-l-sulfonic acid sodium salt2-hexyl-oct-4-ol-l-sulfonic acid potassium salt2-ethyl-tetradec-3-ol-l-sulfonic acid sodium salt2-butyl-dodec-2-ol-l-sultonic acid sodium salt2-hexyl-dec-3-ol-l-sulfonic acid sodium salt tetradec-4-ol-3-sulfonicacid sodium salt hexadec-5-ol-3-sulfonic acid sodium salttetradec-7-ol-6-sulfonic acid sodium salt heXadec-7-ol-6-sulfonic acidpotassium salt 4-ethyl-dodec-4-ol-3-sulfonic acid sodium salt4-ethyl-tetradec-4-0l-3-sulfonic acid sodium salt'undec-8-ol-5-(1'-ethyl methylene sulfonic acid sodium salt)tridec-8-ol-5-(1'-ethyl methylene sulfonic acid sodium salt) itetradec-4-ol-1,2-disulfonic acid-disodium salthexadec-4-ol-1,2-disulfonic acid-disodium salt undec-7-ol-5-sodiumsulfonate-5-(1'-ethyl-methylene sodium sulfonate) The sulfonatecompositions are useful as detergents per se and in combination withother detergent active compounds, builders and adjuvant compounds. Thesematerials are well known in the art.

Other actives useful in conjunction with the present compositionsinclude anionic, nonionic, ampholytic and zwitterionic syntheticdetergents individually and in various combination. Typical otheractives include alkali metal and ammonium salts of higher fatty acids,alcohol sulfates, linear alkyl sulfonates, alkali metal, alkaline earthmetal and ammonium alkaryl sulfonates and fatty alcohol alkoxy sulfates.Typical specific compositions include sodiumdodecylbenzenesulfonate,sodium xylene sulfonate, sodiumnonylphenol ether sulfate (40 percentethylene oxide).

Builders are ordinarily used such as water soluble inorganic alkalinebuilder salts, water soluble organic alkaline 'builder salts, andmixtures thereof. The proportions of builders to such sulfonatecompounds generally range from about 10:1 to about 1:10 by weight, withabout 5:1 to about 1:2 being preferred.

Typical builders for use with olefin sulfonates are well known as, forexample, set forth in U.S. Pat. 3,332,880. They include ammonium oralkali metal borates, carbonates, and phosphates; ammonia or alkalimetal polycarboxylates, alkali metal polyphosphates. Typical buildersare sodium tripolyphosphate, tri-sodium nitrolotriacetate, potassiumethane-l-hydroxy-l,l-diphosphate.

The following examples indicate preferred embodiments of the presentinvention.

EXAMPLE I Vinyl olefins 93.0 Vinylidene olefins 3.7 Internal olefins 3.3

The dodecene was reacted in a laboratory falling film sulfonationreactor system similar to that described in Soap and Chemical Specialty43, 122 (May 1967) using an S olefin molar feed ratio of 1.04. Thereactor was a jacketed tube of mm. internal diameter and 75 cm. length.S0 and nitrogen (5 mol percent S0 were fed as a gaseous phase at thetop. The olefin was also fed at the top and in a liquid phase. Thereactor temperature was 38 to 40 C. The olefin feed rate was 24 gramsper hour per millimeter of internal periphery of the vertically disposedtubular reactor.

The sulfonation efliuent was saponified by reaction at reflux for eighthours with l-normal NaOH solution fed at 50-60 C. The NaOH was used inabout 25 percent excess above the stoichiometric. After saponification,residual oil phase material was removed, then the mixture was cooled andback titrated to neutrality with 1- normal H SO to form product olefinsulfonates.

EXAMPLE II Example I was repeated using a high purity tetradecene cutcontaining 98.0 weight percent C olefins, 1.3 weight 6 percent C olefinsand traces of C and other olefins and paraflins. The olefin mixturecontained an overall distribution (mol percent) on a basis of molecularstructure as determined by nuclear magnetic resonance (NMR) as follows:

Vinyl olefins v 82.0 Vinylidene olefins 10.9 Internal olefins 7.1

The olefins were sulfonated and the product saponified as in Example I,all conditions being the same, with the exception of the olefin feedrate which in this instance was 28 grams per hour per millimeter ofinternal periphery of the vertically disposed tubular reactor.

EXAMPLE III Vinyl olefins 63.0 Vinylidene olefins 27.2 Internal olefins9.8

The olefins were sulfonated as in Example I, all conditions being thesame, with the exception of the olefin feed rate which in this instancewas 32 grams per hour per millimeter of internal periphery of thevertically disposed tubular reactor. The sulfonation product wasconverted to alkali metal salts as in Example I.

EXAMPLE IV The sulfonate products of Examples I, II and III werecombined in various proportions by weight to provide various sulfonatemixtures for testing for washing performance. Data based on the resultsare tabulated in the figure. The curves for the various performancepercentages from 30 percent to percent inclusive are based upon theresults obtained when using the sulfonate products of the Examples I, IIand HI in the approximate proportions mdicated, considering the deoiledsulfonate portion of the product of Example I as all C that of Example Has all C and that of Example III as all C The data for the percent lineof the figure is corrected for the actual proportions of the startingolefins, considering olefins lower than C as C and those higher than Cas C The 90 percent line represents from about 4 to about 33 Wt. percentC sulfonates, from 0 to about 18 percent C sulfonates and from about 60to about 96 percent C sulfonates. The corrected compositions for thepoints A through G of the 90 percent line of the figure are as folows:

Wt. percent The difference between the approximate proportions and theactual proportions is small for the 90 percent performance data andnegligible for the 35-85 percent data. The 30-85 percent data is readilyconverted to an acgial basis using the analysis given in Examples I, IIan III.

The olefin sulfonate mixtures were tested using a standard comparativeDishwashing Test (J.A.O C.S. 43, 576 (1966)) to achieve a standardperformance evaluation. This testing involves comparison to theperformance of a representative standard washing preparation similar tocommercial light duty dishwashing concentrates containing 60 percent LAS(linear alkyl benzene sulfonate, Ultrawet K), 30 percent AES (alcoholethoxy sulfate, Steol 4N) and 10 percent LDEA (lauryl diethanol amide,Ninol AA62 extra). Tests were with water of 50-150 p.p.m. hardness at atemperature of 49 C. using active concentration of 0.045 wt. percent.

The olefin sulfonates (sodium salts) were formulated with a monoethanolamide (Stephen LMMEA) in a ratio of about 4 parts by weight of olefinsulfonates and 1 part of amide.

Results of the test are plotted in the figure, the performance linesindicating percentage based on number of plates washed by the testcomposition relative to the number of plates similarly washed by thestandard composition.

EXAMPLE V The foregoing experiments are repeated with other sulfonationsystems and conditions, including pot type reactors, sprayed chamberreactors, and the like, using saponification under various conditions oftemperature and with various arrangements for immediate and delayedneutralization or hydrolysis of the sulfonation efiluent as a separatestep before complete saponification and using various proportions ofcaustic or alkaline substance ranging from about stoichiometric (1:1)based on the number of moles of sulfonic acid radicals or precursorspresent in the sulfonation efiluent to about a 50 percent excess of molsof caustic or alkaline substance. Olefins sulfonated includesubstantially pure olefins with respect to molecular weight as well ascarbon skeleton structure, as well as sub combinations, for subsequentblending, and also include total compositions for use without requiringsubsequent blending.

We claim:

1. A mixture of water soluble olefin sulfonate salts which results fromsaponifying the reaction product of S and olefins having from about 12to about 16 carbon atoms per molecule, the proportions of C C and C 8olefin sulfonates being within the area defined by the points ABCDEFGAof the figure.

2. The sulfonates of claim 1 further characterized as having from about'12'to about 16 carbon atoms per molecule, averaging from about 14.7 toabout 15.9 carbon atoms per molecule, and containing from 0 to about 15wt. percent of sulfonates having 14 carbon atoms per molecule.

3. The sulfonates of claim 1 further characterized as having from about4 to about 33 percent C sulfonates, from 0 to about 18 percent Csulfonates, and from about to about 96 percent C sulfonates. 1

4. The composition in accordance with claim 1 wherein the olefinsulfonate salts aresalts of sodium. 1 p

5. The composition in accordance with claim 1 wherein the sulfonates aresalts of sodium or potassium.

6. The sulfonates of claim 1 further characterized as being derived frommixed olefins containing from about 60 to about 98 mol percent vinylolefins, from about 1 to about 30 mol. percent vinylidene olefins andfrom about 1 to about 15 mol percent internal olefins.

7. The sulfonates of claim 1 further characterized as being derived frommixed olefins wherein: v V

(a) the C olefins are from about 90 to about 98 mol percent vinylolefins, from about 1 to about 7 percent vinylidene olefins and fromabout 1 to about 7 percent internal olefins,

(b) the C olefins are from about to about mol percent vinyl olefins,from about 5 to about 12 percent vinylidene olefins and from about 5 toabout 12 percent internal olefins, and

(c) the C olefins are from about 60 to about 70 mol percent vinylolefins, from about 20 to about 30 percent vinylidene olefins and fromabout 5 to about 15 percent internal olefins. I

References Cited UNITED STATES PATENTS 3,409,637 11/1968 Eccles et a1260-513 R FOREIGN PATENTS 1,961,963 12/1969 Germany 260-513 R DANIEL D.HORWITZ, Primary Examiner

